Crystal structure of a monoclinic polymorph of 5-amino-1,3,4-thia­diazol-2(3H)-one

Kim, N.; Kang, S.K.

doi:10.1107/S1600536814016055

organic compounds

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Crystal structure of a monoclinic polymorph of 5-amino-1,3,4-thiadiazol-2(3H)-one

Namhun Kim ^a and Sung Kwon Kang ^a ^*

^aDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
^*Correspondence e-mail: skkang@cnu.ac.kr

Edited by E. R. T. Tiekink, University of Malaya, Malaysia (Received 7 July 2014; accepted 9 July 2014; online 1 August 2014)

The title compound, C₂H₃N₃OS, is a monoclinic (P2₁/c) polymorph of the previously reported triclinic structure [Kang et al. (2012 ). Acta Cryst. E68, o1198]. The asymmetric unit contains two independent molecules which are essentially planar, with r.m.s. deviations of 0.001 and 0.032 Å from the mean plane defined by the seven non-H atoms. In the crystal, N—H⋯N and N—H⋯O hydrogen bonds link the molecules into a sheet parallel to (111).

Keywords: crystal structure; polymorph; thiadiazolone; hydrogen bonds.

CCDC reference: 1013072

1. Related literature

For structures and reactivity of thiadiazole derivatives, see: Parkanyi et al. (1989 ); Cho et al. (1996 ). For the triclinic polymorph, see; Kang et al. (2012).

2. Experimental

2.1. Crystal data

C₂H₃N₃OS
M_r = 117.13
Monoclinic, P 2₁ /c
a = 3.8182 (3) Å
b = 10.8166 (7) Å
c = 21.8043 (15) Å
β = 91.015 (4)°
V = 900.37 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.58 mm⁻¹
T = 296 K
0.21 × 0.1 × 0.09 mm

2.2. Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.911, T_max = 0.931
5812 measured reflections
1709 independent reflections
1376 reflections with I > 2σ(I)
R_int = 0.048

2.3. Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.099
S = 1.08
1709 reflections
151 parameters
All H-atom parameters refined
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N11	0.77 (3)	2.12 (3)	2.891 (4)	174 (3)
N7—H7A⋯O13ⁱ	0.86 (3)	2.07 (4)	2.913 (4)	167 (3)
N7—H7B⋯N4ⁱⁱ	0.85 (4)	2.21 (4)	3.048 (4)	171 (3)
N10—H10⋯O13ⁱⁱⁱ	0.84 (3)	2.09 (3)	2.910 (3)	165 (3)
N14—H14A⋯O6^iv	0.91 (4)	2.14 (4)	3.005 (4)	159 (4)
N14—H14B⋯O6	0.73 (4)	2.58 (4)	3.306 (5)	173 (4)
Symmetry codes: (i) x+1, y-1, z; (ii) -x+2, -y+1, -z+1; (iii) -x+1, -y+2, -z+1; (iv) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

CCDC reference: 1013072

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814016055/tk5326sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814016055/tk5326Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814016055/tk5326Isup3.cml

checkCIF report

Structural commentary top

5-Amino-2H-1,2,4-thiadiazolin-3-one heterocycle is an analog of cytosine (Parkanyi et al., 1989). Derivatives of this heterocyclic compound are interesting in the antibacterial activity, potential carcinogenicity, and kinase inhibitor activity (Cho et al., 1996). The title compound, 5-amino-1,3,4-thiadiazol-2(3H)-one (I) is an isomer of 5-amino-2H-1,2,4-thiadiazolin-3-one, which has become an attractive moiety due to potential biological activities. These heterocyclic compounds are potentially good ligands because of N, O, and S atoms which are good donor atoms to both transition metals (Cu, Zn, Cd) and lanthanide metals (Tb and Eu). In our interest to metal complexes with these heterocyclic compounds, the title compound was isolated accidently.

In (I), Fig. 1, two independent molecules comprise the asymmetric unit, which are linked by the intermolecular N—H···N and N—H···O hydrogen bonds. The 1,3,4-thiadiazol-2-one units are almost planar, with r.m.s. deviations of 0.001 – 0.032 Å from the corresponding least-squares plane defined by the seven constituent atoms. The crystal structure is stabilized by the intermolecular N—H···N and N—H···O hydrogen bonds, which link the molecules into a two-dimensional sheet parallel to 111 plane (Table 1 and Fig. 2).

Synthesis and crystallization top

The title compound (I) was synthesized by the process of the previous report (Kang et al. 2012). Copper(II) chloride (1.36 g, 8 mmol) dissolved in ethanol, was added drop wise to a stirred ethanolic solution containing 5-amino-1,3,4-thiadiazol-2(3H-one (1.87 g, 16 mmol). The mixture was stirred for 10 h at room temperature. The resulting solution was filtered and allowed to stand at room temperature. Colourless crystals of (I) were obtained at room temperature over a period of a few weeks.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms of the NH and NH₂ groups were located in a difference Fourier map and refined freely [refined distances = 0.73 (4)–0.91 (4) Å].

Related literature top

For structures and reactivity of thiadiazole derivatives, see: Parkanyi et al. (1989); Cho et al. (1996). For the triclinic polymorph, see; Kang et al. (2012).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and 30% probability ellipsoids. Intermolecular N—H···N and N—H···O hydrogen bonds are indicated by dashed lines.
	Fig. 2. Part of the crystal structure of the title compound, showing molecules linked by intermolecular N—H···N and N—H···O hydrogen bonds (dashed lines).

5-Amino-1,3,4-thiadiazol-2(3H)-one top

Crystal data top

C₂H₃N₃OS	F(000) = 480
M_r = 117.13	D_x = 1.728 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1700 reflections
a = 3.8182 (3) Å	θ = 2.7–25.7°
b = 10.8166 (7) Å	µ = 0.58 mm⁻¹
c = 21.8043 (15) Å	T = 296 K
β = 91.015 (4)°	Block, colourless
V = 900.37 (11) Å³	0.21 × 0.1 × 0.09 mm
Z = 8

Data collection top

Bruker SMART CCD area-detector diffractometer	1376 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
ϕ and ω scans	θ_max = 25.8°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −4→4
T_min = 0.911, T_max = 0.931	k = −12→13
5812 measured reflections	l = −26→26
1709 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	All H-atom parameters refined
wR(F²) = 0.099	w = 1/[σ²(F_o²) + (0.0317P)² + 0.833P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1709 reflections	Δρ_max = 0.37 e Å⁻³
151 parameters	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₂H₃N₃OS	V = 900.37 (11) Å³
M_r = 117.13	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.8182 (3) Å	µ = 0.58 mm⁻¹
b = 10.8166 (7) Å	T = 296 K
c = 21.8043 (15) Å	0.21 × 0.1 × 0.09 mm
β = 91.015 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1709 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1376 reflections with I > 2σ(I)
T_min = 0.911, T_max = 0.931	R_int = 0.048
5812 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.099	All H-atom parameters refined
S = 1.08	Δρ_max = 0.37 e Å⁻³
1709 reflections	Δρ_min = −0.29 e Å⁻³
151 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.5670 (2)	0.33458 (7)	0.36148 (3)	0.0316 (2)
C2	0.4389 (8)	0.4860 (3)	0.33723 (13)	0.0297 (7)
N3	0.5448 (8)	0.5631 (3)	0.38116 (12)	0.0327 (7)
H3	0.487 (9)	0.631 (3)	0.3829 (14)	0.030 (10)*
N4	0.7091 (7)	0.5177 (2)	0.43328 (11)	0.0301 (6)
C5	0.7362 (8)	0.3992 (3)	0.42932 (13)	0.0259 (7)
O6	0.2779 (7)	0.5107 (2)	0.28964 (10)	0.0454 (6)
N7	0.8708 (8)	0.3270 (3)	0.47486 (13)	0.0349 (7)
H7A	0.968 (9)	0.259 (3)	0.4641 (14)	0.035 (10)*
H7B	0.983 (10)	0.364 (3)	0.5033 (17)	0.049 (11)*
S8	0.0629 (2)	1.02405 (7)	0.34352 (4)	0.0334 (2)
C9	0.2461 (8)	1.0171 (3)	0.41853 (13)	0.0294 (7)
N10	0.3361 (7)	0.9003 (2)	0.42943 (12)	0.0315 (6)
H10	0.438 (8)	0.884 (3)	0.4630 (14)	0.024 (8)*
N11	0.2747 (8)	0.8126 (2)	0.38422 (11)	0.0359 (7)
C12	0.1325 (8)	0.8645 (3)	0.33686 (13)	0.0296 (7)
O13	0.2843 (7)	1.1052 (2)	0.45367 (10)	0.0458 (7)
N14	0.0397 (10)	0.8045 (4)	0.28504 (14)	0.0502 (9)
H14A	−0.052 (11)	0.853 (4)	0.2546 (19)	0.068 (13)*
H14B	0.074 (10)	0.738 (4)	0.2852 (17)	0.043 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0410 (5)	0.0227 (4)	0.0307 (4)	0.0018 (4)	−0.0078 (3)	−0.0059 (3)
C2	0.0324 (18)	0.0272 (17)	0.0295 (16)	0.0007 (14)	−0.0021 (13)	−0.0011 (13)
N3	0.0497 (19)	0.0174 (14)	0.0307 (15)	0.0063 (13)	−0.0095 (12)	−0.0019 (11)
N4	0.0401 (16)	0.0220 (14)	0.0278 (13)	0.0087 (12)	−0.0088 (11)	−0.0033 (11)
C5	0.0287 (17)	0.0221 (16)	0.0269 (15)	0.0020 (13)	0.0001 (12)	−0.0042 (12)
O6	0.0609 (17)	0.0390 (14)	0.0355 (13)	0.0025 (12)	−0.0201 (12)	0.0028 (11)
N7	0.0482 (19)	0.0240 (16)	0.0319 (15)	0.0073 (14)	−0.0118 (13)	−0.0026 (13)
S8	0.0422 (5)	0.0250 (4)	0.0326 (4)	0.0077 (4)	−0.0091 (3)	0.0031 (3)
C9	0.0343 (18)	0.0242 (16)	0.0296 (16)	0.0068 (14)	−0.0037 (13)	0.0004 (13)
N10	0.0479 (18)	0.0233 (14)	0.0229 (13)	0.0116 (12)	−0.0093 (12)	−0.0023 (11)
N11	0.0550 (19)	0.0239 (14)	0.0284 (14)	0.0093 (13)	−0.0091 (12)	−0.0033 (11)
C12	0.0358 (19)	0.0242 (16)	0.0288 (16)	0.0051 (14)	−0.0027 (13)	−0.0019 (13)
O13	0.0714 (18)	0.0255 (13)	0.0400 (13)	0.0124 (12)	−0.0154 (12)	−0.0079 (11)
N14	0.079 (3)	0.036 (2)	0.0346 (18)	0.0114 (18)	−0.0230 (16)	−0.0056 (15)

Geometric parameters (Å, º) top

S1—C5	1.749 (3)	S8—C12	1.753 (3)
S1—C2	1.786 (3)	S8—C9	1.769 (3)
C2—O6	1.226 (4)	C9—O13	1.230 (3)
C2—N3	1.328 (4)	C9—N10	1.329 (4)
N3—N4	1.379 (3)	N10—N11	1.385 (3)
N3—H3	0.77 (3)	N10—H10	0.84 (3)
N4—C5	1.289 (4)	N11—C12	1.287 (4)
C5—N7	1.357 (4)	C12—N14	1.345 (4)
N7—H7A	0.86 (3)	N14—H14A	0.91 (4)
N7—H7B	0.85 (4)	N14—H14B	0.73 (4)

C5—S1—C2	88.81 (14)	C12—S8—C9	88.66 (14)
O6—C2—N3	127.9 (3)	O13—C9—N10	126.7 (3)
O6—C2—S1	125.5 (2)	O13—C9—S8	125.7 (2)
N3—C2—S1	106.5 (2)	N10—C9—S8	107.6 (2)
C2—N3—N4	120.0 (3)	C9—N10—N11	118.9 (3)
C2—N3—H3	123 (2)	C9—N10—H10	118 (2)
N4—N3—H3	115 (2)	N11—N10—H10	123 (2)
C5—N4—N3	109.5 (2)	C12—N11—N10	109.6 (2)
N4—C5—N7	123.6 (3)	N11—C12—N14	124.4 (3)
N4—C5—S1	115.1 (2)	N11—C12—S8	115.2 (2)
N7—C5—S1	121.2 (2)	N14—C12—S8	120.4 (3)
C5—N7—H7A	117 (2)	C12—N14—H14A	115 (3)
C5—N7—H7B	116 (2)	C12—N14—H14B	115 (3)
H7A—N7—H7B	113 (3)	H14A—N14—H14B	130 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N11	0.77 (3)	2.12 (3)	2.891 (4)	174 (3)
N7—H7A···O13ⁱ	0.86 (3)	2.07 (4)	2.913 (4)	167 (3)
N7—H7B···N4ⁱⁱ	0.85 (4)	2.21 (4)	3.048 (4)	171 (3)
N10—H10···O13ⁱⁱⁱ	0.84 (3)	2.09 (3)	2.910 (3)	165 (3)
N14—H14A···O6^iv	0.91 (4)	2.14 (4)	3.005 (4)	159 (4)
N14—H14B···O6	0.73 (4)	2.58 (4)	3.306 (5)	173 (4)

Symmetry codes: (i) x+1, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+2, −z+1; (iv) −x, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N11	0.77 (3)	2.12 (3)	2.891 (4)	174 (3)
N7—H7A···O13ⁱ	0.86 (3)	2.07 (4)	2.913 (4)	167 (3)
N7—H7B···N4ⁱⁱ	0.85 (4)	2.21 (4)	3.048 (4)	171 (3)
N10—H10···O13ⁱⁱⁱ	0.84 (3)	2.09 (3)	2.910 (3)	165 (3)
N14—H14A···O6^iv	0.91 (4)	2.14 (4)	3.005 (4)	159 (4)
N14—H14B···O6	0.73 (4)	2.58 (4)	3.306 (5)	173 (4)

Symmetry codes: (i) x+1, y−1, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+2, −z+1; (iv) −x, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the research fund of Chungnam National University.

References

Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cho, N. S., Cho, J. J., Ra, D. Y., Moon, J. H., Song, J. S. & Kang, S. K. (1996). Bull. Korean Chem. Soc. 17, 1170–1174. CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Kang, S. K., Cho, N. S. & Jang, S. (2012). Acta Cryst. E68, o1198. CSD CrossRef IUCr Journals Google Scholar
Parkanyi, C., Yuan, H. L., Cho, N. S., Jaw, J. J., Woodhouse, T. E. & Aung, T. L. (1989). J. Heterocycl. Chem. 26, 1331–1334. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536814016055

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Crystal structure of a monoclinic polymorph of 5-amino-1,3,4-thia­diazol-2(3H)-one

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

Crystal structure of a monoclinic polymorph of 5-amino-1,3,4-thiadiazol-2(3H)-one